Azo dye



Patented June 16, 1942 Azo' DYE Chiles E. Sparks, Wilmington, Del., assignor to A E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application June 25, 1940, Serial No. 342,289

' Claims.

This invention relates to new azo compounds having substantivity to cotton and regenerated cellulose fibers, to insoluble azo compounds which are produced from said substantive compounds, to fibers dyed with said compounds and to processes of making said compounds and dyeings. More particularly the first components of the substantive azo compounds consist of a typeof di(amino-phenoXy-alkyl-acylamino) alkanes and the second components are a type of aryl amines. The substantive disazo compounds are especially useful as bases for developed dyeings, since they are capable of tetrazotization on the fiber and of development with suitable azo dye coupling components.

Various disazo compounds having substantivity for cotton and regenerated cellulose and which can be tetrazotized on the fiber and coupled with coupling components to form dyeings of excellent fastness and good insolubility are known; but in many cases the dyeings developed from such substantive tetrazotizable compounds do not have as good brightness as is desired.

It is among the objects of this invention to provide disazo dyes which are substantive to cotton and regenerated cellulose and which contain terminal primary aryl amino groups. Another object of the invention is to provide such substantive compounds which will give developed dyeings in improved brightness, improved washing fastness, gooddischarge properties and other properties desired in such dyeings, when they are tetrazotized on the fiber and coupled with suitable coupling components. Another object of the invention is to provide improved dyeings resulting from the tetrazotization and development of the described direct dyeings. Other objects of the invention will be apparent from the following description,

The objects of the invention are attained in general by tetrazotizing one of a class of di- (amino-phenoxy-alkyl-acylamino) alkanes and coupling with a class of suitable arylamines, whereby a tetrazotizable azo compound substantive to cotton and regenerated cellulose is produced. This dye is dyed on the fiber, tetrazotized thereon and developed with a suitable dye coupling component which is devoid of solubilizing groups to form the finished dyeing. The substantive dyes are represented in general by the formula wherein D represents a radical of the groups consisting of the polymethylene diamin-es having 2 to 10 methylene groups and straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and is substituted in the methylene groups once to twice the number of methylene groups, a radical of the diamino-cycloalkane series having 4 to 6 carbons in the ring and ring substituted straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and is present once to two less than the number of carbons in the ring, and a radical of the diazacycloalkane series having 3 to 6 carbons in the ring and the straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and is substituted in the ring carbons once to twice the number of carbons in the ring; [C(R) 2] represents the group consisting of straight and branched chain aliphatic radicals wherein R occurs twice as indicated and the symbol R represents like and unlike members of the group consisting of hydrogen and alkyl radicals containing 1 to 6 carbon atoms. Of these aliphatic radicals, there may be 1 to 10 as represented by the subscript n, for example -[C(R)2]n includes such radicals as and where alkyl may be any saturated aliphatic hydrocarbon radical containing 1 to 6 carbon atoms; R, is from the group consisting of hydrogen, alkyl with l to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, halogens, CN, carboxy and sulfonic acid; m is 1 to 4; and YNH2 is the radical of an amino-substituted coupling component from the group consisting of certain arylamines of the benzene and naphthalene series, amino naphthol sulfonic acids, aminophenylamino-naphthol sulfonic acids, amino-benzoylamino-naphthol sulfonic acids, amino-benzoylamino-benzoyl-amino-napthol sulfonic acids and amino-phenyl pyrazolones.

The invention will be more fully set forth in appearance and substantivity for cotton and the following more detailed description which insimilar fibers. The product is represented by eludes examples that are given as illustrative emthe formula N O-CHrfil-NH-CH:CH:NH+fiOHz-O-Ifil i i 0 N bodiments of the invention and not as limitations Five pa-rts'of cotton piece goods were dyed thereof. Parts are expressed in parts by weight from a water solution of the compound in the unless otherwise noted. usual manner known to those skilled in the art, Example I using two-tenths parts of the dye. The dyed fabric was rinsed in cold water and then put into A slurry was made consisting of 143 parts of 2000 parts of water at 20 C. The compound was 1,2-di(4-amino-phenoxy-acetylamino) ethane tetrazotized on the fiber by adding three'parts of and 2000 parts of water. It was acidified by addsodium nitrite and four parts of sulfuric acid to ing 73 parts of 100% hydrochloric acid as a the water and stirring for 15 minutes. The piece solution. The mixture was cooled by adding ice was rinsed with cold water and then put into a to 0 C. and parts of sodium nitrite 05 solution which was made by dissolving one part were then added. Tetrazotization was continued of beta-naphthol in 2000 parts of water and oneat 0-5 C. for hour whilst maintaining a slight half part of caustic soda. The solution was excess nitrite. stirred rapidly while adding the rinsed piece A slurry containing 295 parts of 2(3'-aminogoods and stirring was continued for 15 minutes. benzoylamino)-5-naphthol-7-sulfonic acid and 30 The fabric was then rinsed in cold water and 2000 parts of water was made. Anaqueous soludried. The dyeing was a scarlet shade. The tion of ammonia in sufiicient quantity for comdye on the fiber is represented by the formula I N N plete solution and a slightly alkaline reaction to 5 Example II Brilliant Yellow paper was added and then 7 parts of sodium-bicarbonate were added. The solu- A dye represented by the formula 1,2-di-(4'- tion was cooled to 0 C. and parts of sodiumamino-phenoxy-acetylamino) -ethane: (1-(3- carbonate were added. aminophenyl) -5-pyrazolone-3-carboxylic acid)z The solution of the tet azo 00 1 0111101 Was 55 was preparedby aprocedure similar to Example I slowly added to the cold alkaline solution of 2-(3- except that parts of 1-(3-amino-phenyl)-5- amino-benzoyl-amino) 5 naphthol '7 su fonic pyrazolone-3-carboxylic-acid were used instead acid. The coupling mixture was stirred one hour of 295 parts of 2-(3-amino-benzoyl-amino) -5- after the totrazo mixture had been added whilst naphthol-7-sulfonic acid. The resulting dye was an excess of e Co p i Component Was present 0 an orange powder, and had properties similar to and alkalinity with sodium carbonate was mainth b t ti compound of Exalnple I It is tained. The suspension was then heated to represented by the formula N N I NH: HzN- '70-80 C., salted 5% with sodium chloride and When dyed and developed on the fiber with filtered. The precipitate was dried at 80-85 C. beta naphthol in a manner similar to that dein an oven. The dry product had an orange 75 scribed in Example I the dyeing was an orange shade. The structure of the dye on the fiber is represented by the formula When dyed on cotton fiber and developed with beta naphthol in a manner similar to that de- Example III A dye represented by the formula l,4=-di(4'- amino-phenoxy-acetyl) -piperazine ;[2(Y-amino" scribed in Example I the dyeing was a red shade. The dye on the fiber is represented by the formula CHaCH:

benzoylamino) -5-naphthol-'7-sulfonic acidlz was O C made by following the procedure of Example I L I; ll N except that 153.5 parts of 1,4-di(4-aminophenoxy-acetyl) D11 Je1aZlne was used instead of 143 Naoas O: HN SOaNa parts of 1,2-d1(4 -am1nophenoxy-acetylammo) ethane and 295 parts of 2-(4'-amino-benzoylamino) -5-naphthol-' 7-sulfonic acid was used instead of 295 parts of 2-(3-amino-benzoylamino) OH OH B-naphthol-l-sulfonic acid. The product in the form of a dry powder had an orange appearance N and its other properties were similar to those of M 1| the product of Example I. The product is rep- N N resented by the formula OH OH CHaCHa N ooHl-o-N N-C-CHz-O N I1 I! H II N O OH: H: O N

The following products were prepared by meth- Naoasr NH C=0 O:C HN SOaNa ods similar to those of the foregoing examples. I The properties of these products were in general similar to the products of the foregoing examples except for variations in shade. The shades OH OH listed opposite each product are the shades of the dyeings on cotton when developed with the component indicated.

- Developed Example Combination with Shade IV 1,2-di(4"-aminophenoxy-acetylamin0)-ethane :4 (2-amino-5- Beta naphthoL- Bordeaux.

naphthol-7-sulfonic acidh. V 1, 2-di(4-aminophenoxy-acetylan lno)-ethane :K [2(4-amino-3- do Maroon.

sulfo-phenylamino)-5-naphthol-7-sulfonic acidh. VI 1, 2-di(4-a1nino-2-sulfo-phenoxy-acetylamino)ethane (2-aminodo Red.

5-naphthol-7-sulf0nic acidh. V11 1, 2-cli(4-amino-2-sulfo-phcn0Xy-acetylamin0)-ethane:[2(3-aminodo Orange.

henzoylarnino)-5-naphthol-7-sulf0nic-acidlz. VIII l, 2-di(4-amino-2-sulfo-phenoxy-acetylamino)ethane 2, [2(4- do Do,

amino-benzoylamino)-5-naphthol-7sulfonic acidh. IX 1, 2-di(4'-amino-2-sulfophenoxy-acetylamino)-ethane [1(3- do Yellow.

aminophenyl)-5-pyrazolone-3-carboxylic acidh. X l,2-(li(4-arnin0-2'-sulEo-phenoxy-acetylamino)-ethane 1:3 [2-(4- do Maroon.

amino-3-sulfo-phenylamino)-5-naphthol-7-sulfonic acidlz. XI 1, 2-di(4-amino-2-sulfo-phenoxy-acetylamino)ethane 3 (lamino- .d0 Brown.

naphthalene-G-sulfonic acidh. XII 1, 2-di(4'-amino-2-methoxy-phenoxy-acetylamino)-ethane 3 [2-(3- Scarlet.

amino-benzoylamino)-5-naphthol-7-sulionic acidh. XIII l, 2-di(4-amin0-2'-mcthoxy-phenoxy-acetylamino)-cthane 3 (2- Maroon.

amino-5-11aphthol-7-su]fonlc acid. XIV 1,i rdi-(3-amino-2-methyl-phenoxy-acetylamlno)-ethane :3 [l-(3- Yellow.

amlnophenyl)-5-pyrazolone-B-carboxylic acidh. XV 1, 2-dl(3-amino-2-methy1phenoxy-acetylamino)ethane 3 [2-(3- Scarlet.

amino-benzoylamino)-5-naphtho1-7-su1ionic acidh. XVI l,2 di(3-amino-2-rnethyl-phenoxy-acetylamino)-cthane 3 (2- Maroon.

amino-5-naphthol-7-sulfonic acidh. XVII l,2-di(3-amino-2-methy1-phenoxy-acetylamino)-ethaue 3 (1- D amino-5-naphthol-7-sulfonic acid) XVIII l,2-di(3'-amino-2-rnethyl-phenoxy-acetylamino)ethane 1T2, [2-(4'- Rubine.

amino-3'-su1fo-phe11ylamino)-5-naphth0l-7-su1fonic acidh. XIX l,Z-di(3'-aminophenoxy-acetylamino)-ethane :2 [2-(3-amlno-ben- Orange.

zoylamlno)-5-naphth0l-7-sulfo11lc acidh. XX 1, 2-di(3-aminophenoxy-acetylamino)ethane (2-amino-5-naph- Maroon.

tho1-7-su1lonic acidh. XXI 1, 2di(4-amino-2-chloro-phenoxy-acetylamino)ethane 1:: [2-(3- Scarlet.

amino-benzoylamino)-5-naphthol-7-sulfonic acidh. XXII 1,2-di(4-amino-2-chloro-phenoxy-acetylamino)-ethane I", (2- Maroon.

amino-5-naphthol-7-sulfonic acid) XXIII .l 1, 2-di(4-amino-2-sulf0-phenoxy-acetylamlno)ethane 3 (l-amlno- Brown.

naphthalene.

Example Combination agg Shade 1,2-di(4-amino-2-su1fo-phenoxy-acetylamino)-etl1ane 2 (2- Beta naphthoL. Brown.

methoxy-5-methyl-aniline)z. 1, 2-di(4'-aminopl1enoxy-acetylamino)ethane ":2, [2-(4(4-amino- .do Scarlet.

benzyol)-amino-benzoylamino)-5-naphthol-7-sulfonic acidh. 1, 2-di(4-aminopl1enoxy-acetylamino)ethane :i (l-aminonaphthado Brown.

lene-fi-sulfonic acid)2. 1,2-di(4'-aminopl1en0xy-acetylam1no)-ethane 2 (1-amino-2- do Do.

methoxy-naphthelene-S-sulfonic acidh. l, 2-di(4-aminophenoxy-acetylamino)-ethane (l-amino-8-naph- -do. Do.

thol-3, G-disulfonic acidh. 1,fi-di(4-aminophenoxy-acetylamino)hexane:[l-(3-amu1ophenyl)- do Orange.

5-pyrazolone-3-carb0xylic ac1d]2. I XXX 1,6-di(4-aminophenoxy-acetylam no)-hexane :;[2-(3-am1no-benzoyld Scarlet.

amino)--naphtho1-7-su1fon1c acidh. XXXI 1, G-di(4-aminophenoxy-acetylamino)-11exane 2:, (2-amino-5-naphdo Maroon.

thol-7-sulfonic acidh. XXXII 1, G-di(4-arninophenoxy-acotylamino)hexane :3, (l-amino-E-naphdo Do.

th0l-7-sulfonic acidh. XXXIII 1, 6-di(4-aminopl1enoxy-acetylammo)hexane 2 [2-(4-amino-3- .do Rublne.

sulfo-phenyl-amino)-5-naphthol-7-su.lfonic acidlz. XXXIV 1, 2-di(4-eminophenoxy-acetylamino)-ethane :[2(3-amino-benz0yldo Scarlet.

amino-5-naphtl1ol-7-sulfonic acidlz. XXXV 1, 4-di(4-aminophenoxy-acetyl)-p1perazine 3 [2-(4-am1no-3-sulfodo Blue.

phenylamino)-5-11aphthol-7-sulfonic acldh. XXXVI..." 1,elhdi(e ainiggphenoxy-acetyl)-piperazine2(l-anin1o-5-I1apl1thol-7- do Bordeaux.

5 ionic aci 2. ,XXXVIIHU 1, i-ldfi(4-amin phenoxy-acetyl)-piperazinc: (2-amino-5-naphthol-7- do Blue.

s onic acid 2. XXXVIII 1, 4-di(4'-aminophenoxy-acetyl)-piperazine 2 [1-(3-amin0phenyl)- do Orange.

5-pyrezolene-3-carboxylic aeidlz. XXXIX 1, 4-di(4-aminophenoxy-acetyl)-pipcrazine :(2-am1no-5-naphthol-l- ..do Blue.

sulfonic acid. I XL 1, 4-di(4-aminophenoxy-acetylarnmo)-cyclohexane :3 [l-(3-am1nodo Orange.

phenyl)-5-pyrazolene-3-oarboxylic acidh. XLI 1, 4-di(4-aminophenoxy-acetylamino)-cycl0hexane 2 [2(3-aminodo Scarlet.

benzoylamino)-5-naphthol-7-sulfonic acidh. XLII V 1,2-di(4-aminopl1enoxy-acetylamino)-ethane [l-(3-amino- Phenyl-methyl- Yellow.

phenyl)-5-pyrazolone-3-carboxylic acidh. pyrazolone. XLIII do Meta-toluylene- Orange.

diamine. XLIV do Acgto-acetanil- Yellow.

1 e. XLV 1,2-di(4-aminophenoxy-acetylainino)-ethane 2 (2-amino-5-napl1- Phenyl-methyl- Red.

thol-7-sulfonic acid)z. pyrazolone. XLVI do Meta-toluylene- Violet.

diamine. U XLVII d0 Aceto-aoetanll- Red ide. brown. XLVIII 1, 2-di(4-aminophenoxy-acetylarnino)ethane :t [2-(4-arnino-ben- Phenyl-methyl- Scarlet.

zoylamino)-5-naphthol-7-sulfonic acidh. pyrazolone. XLIX. d0 Meta-toluylene- Red.

diamine. V L do Acgto-acetanil- Scarlet.

Many other compounds can be used for the first components to make products having properties similar to the foregoing products which are represented by the general formula heretofore given. As representative of such first components, the following are mentioned:

1 ,2-di (4-aminophenoxy-acetlyamino) -ethane,

1,6-cli- (3'-aminophenoxy-acetylamino) -hexane,

1,2-di(4=-amino-2-chloro phenoxy acetylamino) -ethane,

1,2-di[a.lpha- (4-amino-2'-methoxy phenoXy) propionylamino] -propane,

1,3di[alpha (3'-arnino-phenoxy) -butyrylaminol butane,

1 ,e-di (4-aminophenoXy-acety1) -piperazine,

1,2-cli(3'-arninophenoXy-acety1) 3,5 dimethy1- pyrazolioline,

1,4-di(4-aminophenoxy acetyl) ethylene trimethylene-diamine,

1,5-di(3-aminophenoXy-acetyl) bis trimethylene-cliamine,

1,4-di(4-amino-phenoxy-acetylamino) -butane,

1 ,10-di alpha- (4'-amino-phenoXy-propionylamino) l-decane,

1,3-di[alpha(3' amino-phenoxy heptanoylamino) l-propane,

1,3-di[beta(3'-amino-phenoxy butyrylamin0)lheptane,

1,2-di(4'-amino-2-sulfophenoxy-acetylamino) ethane,

1,2-di(4'-amino-phenoxy-acetylamino) 1,2 dimethyl-ethane,

1,2-di[beta- (4'-amino phenoxy propionylamino) -ethane,

and

wherein R and m have the values heretofore defined, R" is from the group consisting of hydrogen, alkyl, and alkoxy, 7c is 1 to 2 and the symbol H denotes the coupling position.

(2) Amino naphthol sulfonic acids represented by the formula R! (RIOk in which one R is hydrogen and the other is hydroxy and the M which is meta to hydroxy is SO3H and the other is hydrogen.

(3) Amino-phenyl amino naphthol sulfonic acids represented by the formula NHz M! NH--( I R!!! (4) Amino benzoylamino naphthol sulfonic acids and amino benzoylamino benzoylaminonaphthol sulfonic acids represented by the for- (5) Amino phenyl pyrazolones represented by the formula HiC-C-R l ne t amino-8naphthol-3,5-disulfonic acid, l-amino- 8-naphthol-4-sulfonic acid, 1-amino-5-naphthol- 7-sulfonic acid, 2-amino-S-naphthol-G-sulfonic acid, 1-amino-5-naphthol, 2-(3 '-amino-benzoylamino) -5-naphthol-7-sulfonic acid, 1-(4'-aminobenzoylamino) -5-naphthol-7-sulfonic acid, 2E4- (4-amino benzoylarnino) benzoylaminol 5- naphthol-7-sulfonic acid, 1-(4-amino-benzoylamino) -8-naphthol-4-sulfonic acid, 1- (4'-aminophenyl)-5-pyrazol0ne-3-carboxylic acid, 1-(3- aminophenyl) -3-methyl-5-pyrazolone, 1- (4-amino-phenyl)-3-methyl-5-pyrazolone, 1 (2 methoxy-5-amino-phenyl) -3-methy1-5-pyrazo1one, 1- (4-amino-3'-carboxy-phenyl) 3 methyl 5- pyrazolone, 1- (4-amino-3'-sulfo-phenyl) -5- pyrazolone-3-carboxylic acid, 1-(2-methyl-5-amino-phenyl) 3 methyl 5 pyrazolone, 1 (2'- rnethyl-5"-amino-phenyl) -5-pyrazolone 3 carboxylic acid and 1-(2"-chloro-5-amino-pheny1)- 5-pyrazo1one-3-carboxylic acid.

The substantive dyes contain at least two solubilizing groups such as carboxyl and sulfonic acid but more can be present.

As developing components l-phenyl-3-methyl- 5-pyrazolone, meta-toluylene diamine or acetoacet anilide can be used as well-as beta naphthol. These coupling components produce developed dyeings having similar superior fastness discharge and brightness properties as those produced by developing with beta naphthol and variations in shade can be attained by selection of the coupling component.

The first components of the azo compounds can be made by condensing a diamino alkane, a

, diamino-cyclo-alkane or a diaza-cyclo-alkane of the kinds described, such as a compound represented generally by the formula NH2-DNH2 with a nitro acyl halide of the type and then reducing the nitro groups of the di- (nitro phenoxy acylamino) -alkane, -cyclo-alkane or diaza-cyclo-alkane to amino. In general the condensation can be carried out readily at about 10-to .20 C. in the presence of a basic condensing agent such as an alkali metal'hydroxide and in a medium comprising a non-reactive organic solvent, such as ethylene dichloride. The primary diamines formed after reduction of the nitro groups can then be separated and the products can betetrazotized by methods which are in general well known in the art.

-' The tetrazotizable products are substantive to cotton, regenerated cellulose, various vegetable fibers and similar dyeable substances. When they are tetrazotized and developed on the fiber with the described azo dye coupling component they have excellent fastness to washing, they do not appreciably stain associated undyed fibers during'washing and they have good general properties which are desirable in dyed fibers. When developed on the fibers the brightness of the dyeing is superior as compared with dyeings of like shade which are made with quite similar dyes which do not contain the phenoxy group. For example a dyeing on cotton made with 1,2-di(4- amino-phenoxy-acetylamino)-ethane and developed with beta naphthol is brighter than one made on cotton with 1,2-di(4-aminobenzoylgtrlriinobethane and developed with beta naphinvention is not restricted to the specific illustrations thereof herein set forth.

I claim:

1. An azo compound represented by the formula in which D represents a radical of the group consisting of the polymethylene diamines having 2 to methylene groups and the straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and in which the methylene groups are substituted once to twice the number of methylene groups, a radical of the diamino-cyclo-alkane series having 4 to 6 carbons in the ring and the monoand di-methyl derivatives thereof, and a radical of the diazacyclo-alkane series having 3 to 6 carbons in the ring and the monoand di-methyl derivatives thereof; n is 1 to 6; each R is from the group consisting of hydrogen, alkyl having 1 to 6 carbons, the corresponding alkoxy groups, halogen, CN, carboxy and sulfonic acid; m is 1 to 4; and each YNH2 is the radical of a coupling component from the group consisting of arylamines of the benzene and naphthalene series, amino naphthol sulfonic acids, amino-phenyl-aminonaphthol sulfonic acids, amino-benzoylaminonaphthol sulfonic acids, amino-benzoylaminobenzoyl amino naphthol sulfonic acids and amino-phenyl pyrazolones.

2. An azo compound represented by the formula dam in which D represents a radical of the group consisting of the polymethylene diamines having 2 to 10 methylene groups and the straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and in which the methylene groups are substituted once to twice the number of methylene groups, a radical of the diamino-cyclo-alkane series having 4 to 6 carbons in the ring and the monoand dimethyl derivatives thereof, and a radical of the diazarcyclo-alkane series having 3 to 6 carbons in the ring and the monoand di-methyl derivatives thereof; n is 1 to 6; each R is from the group consisting of hydrogen, alkyl having 1 to 6 carbons, the corresponding alkoxy groups, halogen, CN, carboxy and sulfonic acid; m is 1 to 4; and each YNH2 is the radical of a coupling component of the benzene and naphthalene series from the group which is represented by the following formulae,

hydroxy'; the M which is meta to hydroxy is SO3H and the other ishydrogen; and R is one of a group consisting of-alkyl having 1 to 6 carbons and carboxyl; said compound having at least two solubilizing groups.

3. The 9.20 compound represented by the for- NHa IITH: moss NH-E-O C f)-HN- s OaNa 4. The 2.20 compound represented by the for- 5. The azo compound represented by the formula.

CHzOHz N-OO-C Hz-C-N N-OO Hz-OON 1% g CH2 (Ha 1% taja-swNH-(ko E Q Q 0 NE: NH:

CHILES E. SPARKS.

CERTIFICATE OF CORRECTION.

' June 16, 19h2.

Patent No. 2,286,591.

' CHILES E. SPARKS.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, sec- 0nd column, 'line LLZ, before the word "component" insert "coupling"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this hth day of August, A. D. 1911.2.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents. 

